DE102009009277B4 - Organic electronic device, process for its production and use of compounds - Google Patents

Abstract

wobei für die verwendeten Symbole und Indizes gilt:
Y ist bei jedem Auftreten gleich oder verschieden eine Einfachbindung oder eine bivalente Gruppe, ausgewählt aus der Gruppe bestehend aus B(R¹), C(R¹)₂, NR¹, O, S, C(=O), C(=C(R¹)₂, S(=O), S(=O)₂, P(=O)(R¹)₂, oder einem bivalenten aromatischen oder heteroaromatischen Ringsystem mit 5 bis 18 aromatischen Ringatomen, welches mit einem oder mehreren Resten R¹ substituiert sein kann;
R ist bei jedem Auftreten gleich oder verschieden, D, F, Cl, Br, I, CHO, N(R¹)₂, N(Ar)₂, C(=O)Ar, P(=O)(Ar)₂, S(=O)Ar, S(=O)₂Ar, CR¹=CR¹Ar, CN, NO₂, Si(R¹)₃, B(OR¹)₂, B(R¹)₂, B(Ar)₂, B(N(R¹)₂)₂, OSO₂R¹, eine geradkettige Alkyl-, Alkoxy- oder Thioalkoxygruppe mit 1 bis 40 C-Atomen oder eine geradkettige Alkenyl- oder Alkinylgruppe mit 2 bis 40 C-Atomen oder eine verzweigte oder cyclische Alkyl-, Alkenyl-, Alkinyl-, Alkoxy- oder Thioalkoxygruppe mit 3 bis 40 C-Atomen, die jeweils mit einem oder mehreren Resten R¹ substituiert sein kann, wobei eine oder mehrere nicht benachbarte CH₂-Gruppen durch R¹C=CR¹, C=C , Si(R¹)₂, Ge(R¹)₂, Sn(R¹)₂, C=O, C=S, C=Se, C=NR¹, P(=O)(R¹), SO, SO₂, NR¹, O, S oder CONR¹ ersetzt sein können und wobei ein oder mehrere H-Atome durch D, F, Cl, Br, I, CN oder NO₂ ersetzt sein können, oder ein aromatisches oder heteroaromatisches Ringsystem mit 5 bis 60 aromatischen Ringatomen, das jeweils durch einen oder mehrere Reste R¹ substituiert sein kann, oder eine Aryloxy- oder Heteroaryloxygruppe mit 5 bis 60 aromatischen Ringatomen, die jeweils durch einen oder mehrere Reste R¹ substituiert sein kann, oder eine Kombination dieser Systeme;
R¹ ist bei jedem Auftreten gleich oder verschieden H, D, F, Cl, Br, I, CHO, N(R²)₂, N(Ar)₂, C(=O)Ar, P(=O)(Ar)₂, S(=O)Ar, S(=O)₂Ar, CR²=CR²Ar, CN, NO₂, Si(R²)₃, B(OR²)₂, B(R²)₂, B(N(R²)₂)₂, OSO₂R², eine geradkettige Alkyl-, Alkoxy- oder Thioalkoxygruppe mit 1 bis 40 C-Atomen oder eine geradkettige Alkenyl- oder Alkinylgruppe mit 2 bis 40 C-Atomen oder eine verzweigte oder cyclische Alkyl-, Alkenyl-, Alkinyl-, Alkoxy- oder Thioalkoxygruppe mit 3 bis 40 C-Atomen, die jeweils mit einem oder mehreren Resten R² substituiert sein kann, wobei eine oder mehrere nicht benachbarte CH₂-Gruppen durch R²C=CR^2, C≡C , Si(R²)₂, Ge(R²)₂, Sn(R²)2, C=O, C=S, C=Se, C=NR², P(=O)(R²), SO, SO₂, NR², O, S oder CONR² ersetzt sein können und wobei ein oder mehrere H-Atome durch D, F, Cl, Br, I, CN oder NO₂ ersetzt sein können, oder ein aromatisches oder heteroaromatisches Ringsystem mit 5 bis 60 aromatischen Ringatomen, das jeweils durch einen oder mehrere Reste R² substituiert sein kann, oder eine Aryloxy- oder Heteroaryloxygruppe mit 5 bis 60 aromatischen Ringatomen, die durch einen oder mehrere Reste R² substituiert sein kann, oder eine Kombination dieser Systeme;
Ar ist bei jedem Auftreten gleich oder verschieden ein aromatisches oder heteroaromatisches Ringsystem mit 5 bis 30 aromatischen Ringatomen, das mit einem oder mehreren nicht-aromatischen Resten R¹ substituiert sein kann; dabei können auch zwei Reste Ar, welche an dasselbe Stickstoff- oder Phosphoratom binden, durch eine Einfachbindung oder eine Brücke, ausgewählt aus B(R²), C(R²)₂, Si(R²)₂, C=O, C=NR², C=C(R²)₂, O, S, S=O, SO₂, N(R²), P(R²) und P(=O)R², miteinander verknüpft sein;
R² ist bei jedem Auftreten gleich oder verschieden H, D oder ein aliphatischer, aromatischer und/oder heteroaromatischer Kohlenwasserstoffrest mit 1 bis 20 C-Atomen, in dem auch H-Atome durch F ersetzt sein können;
n ist 0, 1, 2, 3, 4, 5 oder 6;
m ist 1, 2 oder 3, und wobei die organische elektronische Vorrichtung eine organische Elektrolumineszenzvorrichtung (OLED) oder eine lichtemittierende elektrochemische Zelle (LEC) darstellt.Organic electronic device containing cathode, anode and at least one organic layer which is arranged between cathode and anode and which contains at least one compound according to formula (3), formula (4), formula (5) or formula (6),

where the following applies to the symbols and indices used:
In each occurrence, Y is, identically or differently, a single bond or a divalent group selected from the group consisting of B(R ¹ ), C(R ¹ ) ₂ , NR ¹ , O, S, C(=O), C(= C(R ¹ ) ₂ , S(=O), S(=O) ₂ , P(=O)(R ¹ ) ₂ , or a divalent aromatic or heteroaromatic ring system with 5 to 18 aromatic ring atoms, which with one or more R ¹ may be substituted;
R is the same or different in each occurrence, D, F, Cl, Br, I, CHO, N(R ¹ ) ₂ , N(Ar) ₂ , C(=O)Ar, P(=O)(Ar) ₂ , S(=O)Ar, S(=O) ₂ Ar, CR ¹ =CR ¹ Ar, CN, NO ₂ , Si(R ¹ ) ₃ , B(OR ¹ ) ₂ , B(R ¹ ) ₂ , B (Ar) ₂ , B(N(R ¹ ) ₂ ) ₂ , OSO ₂ R ¹ , a straight-chain alkyl, alkoxy or thioalkoxy group with 1 to 40 C atoms or a straight-chain alkenyl or alkynyl group with 2 to 40 C- Atoms or a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy or thioalkoxy group with 3 to 40 carbon atoms, which can each be substituted with one or more radicals R ¹ , one or more non-adjacent CH ₂ groups by R ¹ C=CR ¹ , C=C , Si(R ¹ ) ₂ , Ge(R ¹ ) ₂ , Sn(R ¹ ) ₂ , C=O, C=S, C=Se, C=NR ¹ , P(=O)(R ¹ ), SO, SO ₂ , NR ¹ , O, S or CONR ¹ can be replaced and one or more H atoms can be replaced by D, F, Cl, Br, I, CN or NO ₂ can be replaced, or one aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, each of which can be substituted by one or more R ¹ radicals, or an aryloxy or heteroaryloxy group with 5 to 60 aromatic ring atoms, each of which can be substituted by one or more R ¹ radicals, or a combination of these systems;
R ¹ is the same or different in each occurrence as H, D, F, Cl, Br, I, CHO, N(R ² ) ₂ , N(Ar) ₂ , C(=O)Ar, P(=O)(Ar ) ₂ , S(=O)Ar, S(=O) ₂ Ar, CR ² =CR ² Ar, CN, NO ₂ , Si(R ² ) ₃ , B(OR ² ) ₂ , B(R ² ) ₂ , B(N(R ² ) ₂ ) ₂ , OSO ₂ R ² , a straight-chain alkyl, alkoxy or thioalkoxy group with 1 to 40 carbon atoms or a straight-chain alkenyl or alkynyl group with 2 to 40 carbon atoms or a branched one or cyclic alkyl, alkenyl, alkynyl, alkoxy or thioalkoxy group with 3 to 40 C atoms, each of which can be substituted with one or more R ² radicals, where one or more non-adjacent CH ₂ groups are replaced by R ² C =CR ^2, C≡C , Si(R ² ) ₂ , Ge(R ² ) ₂ , Sn(R ² )2, C=O, C=S, C=Se, C=NR ² , P(=O )(R ² ), SO, SO ₂ , NR ² , O, S or CONR ² can be replaced and one or more H atoms can be replaced by D, F, Cl, Br, I, CN or NO ₂ , or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, each of which may be substituted by one or more R ² radicals, or an aryloxy or heteroaryloxy group with 5 to 60 aromatic ring atoms, which may be substituted by one or more R ² radicals , or a combination of these systems;
In each occurrence, Ar is, identically or differently, an aromatic or heteroaromatic ring system with 5 to 30 aromatic ring atoms, which may be substituted with one or more non-aromatic radicals R ¹ ; Two Ar residues, which bind to the same nitrogen or phosphorus atom, can also be formed through a single bond or a bridge, selected from B(R ² ), C(R ² ) ₂ , Si(R ² ) ₂ , C=O, C =NR ² , C=C(R ² ) ₂ , O, S, S=O, SO ₂ , N(R ² ), P(R ² ) and P(=O)R ² , be linked together;
In each occurrence, R ² is identical or different H, D or an aliphatic, aromatic and/or heteroaromatic hydrocarbon radical with 1 to 20 carbon atoms, in which H atoms can also be replaced by F;
n is 0, 1, 2, 3, 4, 5 or 6;
m is 1, 2 or 3, and wherein the organic electronic device is an organic electroluminescence device (OLED) or a light-emitting electrochemical cell (LEC).

Description

The present invention relates to organic electronic devices, in particular organic electroluminescent devices, which contain aromatic nitrogen heterocycles.

The construction of organic electroluminescence devices (OLEDs), in which organic semiconductors are used as functional materials, is, for example, in US 4,539,507 A , US 5,151,629 A , EP 0 676 461 A2 and WO 98/27 136 A1 described. However, further improvements are desirable before these devices can be used for high-quality, long-lasting displays. There is currently still a need for improvement, particularly in terms of the service life, efficiency and operating voltage of organic electroluminescent devices. Furthermore, it is necessary that the compounds have high thermal stability and can be sublimated without decomposition.

Improvements are particularly desirable in the charge injection and transport materials, since the properties of the charge transport materials also have a significant influence on the above-mentioned properties of the organic electroluminescent device. In particular, there is a need for improvement in electron transport materials and hole injection or hole transport materials, which at the same time lead to good efficiency, long service life and low operating voltage. The properties of these materials in particular often limit the service life, efficiency and operating voltage of the organic electroluminescent device.

AlQ ₃ has long been used as an electron transport material (e.g. US 4,539,507 A ), however, has several disadvantages: It cannot be vapor-deposited without leaving any residue because it partially decomposes at the sublimation temperature, which is a major problem, especially for production systems. This means that the vapor deposition sources have to be cleaned or changed again and again. Furthermore, decomposition products of AlQ ₃ get into the OLED, which contribute to a reduced service life and reduced quantum and power efficiency. AlQ ₃ also has low electron mobility, which leads to higher voltages and therefore lower power efficiency. In order to avoid short circuits in the display, one would like to increase the layer thickness; This is not possible with AlQ ₃ because of the low charge carrier mobility and the resulting increase in voltage. The charge carrier mobility of other electron conductors ( US 4,539,507 A ) is also too low to build up thicker layers with it, although the lifespan of the OLED is even worse than when using AlQ ₃ . The inherent color (yellow in the solid) of AlQ ₃ also proves to be unfavorable, which can lead to color shifts due to reabsorption and weak re-emission, especially in blue OLEDs. Here, blue OLEDs can only be displayed with severe losses in efficiency and color location.

In addition to various triarylamine derivatives or carbazole derivatives, hexaazatriphenylene derivatives, especially those substituted with cyano groups, are used as hole injection or hole transport materials in organic electroluminescence devices according to the prior art (e.g. WO 01/049 806 A1 or DE 10 2005 043 163 A1 ). There is also a need for further improvement in terms of service life, efficiency and operating voltage.

There is therefore still a need for electron transport materials and hole injection or hole transport materials that lead to good efficiencies and at the same time long service lives in organic electroluminescent devices. It has now surprisingly been found that organic electroluminescent devices which contain certain nitrogen heteroaromatics - listed below - as electron transport materials or as hole injection or hole transport materials, have significant improvements compared to the prior art. With these materials it is possible to achieve high efficiencies and long service lives at the same time.

K. Tagami et al. Nano Letters, Vol. 4, 2004(2), pp. 209 - 212 describes the quantum transport properties of azaphenalene derivatives. Heptaazaphenalene derivatives, especially those substituted with aromatic groups, alkoxy groups or amino groups, are already known in the literature (e.g. E. Horvath-Bordon et al. Dalton Trans., 2004, pp. 3900 - 3908 ); they are used as protection against UV radiation (e.g. WO 2007/006 807 A1 ) or as a flame retardant (e.g. WO 01/021 698 A1 ) used. The use of such compounds in organic electronic devices is not known.

wobei für die verwendeten Symbole und Indizes gilt:

• Y ist bei jedem Auftreten gleich oder verschieden eine Einfachbindung oder eine bivalente Gruppe, ausgewählt aus der Gruppe bestehend aus B(R¹)₂, C(R¹)₂, NR¹, O, S, C(=O), C(=C(R¹)₂, S(=O), S(=O)₂, P(=O)(R¹)₂, oder einem bivalenten aromatischen oder heteroaromatischen Ringsystem mit 5 bis 18 aromatischen Ringatomen, welches mit einem oder mehreren Resten R¹ substituiert sein kann;
• R ist bei jedem Auftreten gleich oder verschieden D, F, Cl, Br, I, CHO, N(R¹)₂, N(Ar)₂, C(=O)Ar, P(=O)(Ar)₂, S(=O)Ar, S(=O)₂Ar, CR¹=CR¹Ar, CN, NO₂, Si(R¹)₃, B(OR¹)₂, B(R¹)₂, B(Ar)₂, B(N(R¹)₂)₂, OSO₂R¹, eine geradkettige Alkyl-, Alkoxy- oder Thioalkoxygruppe mit 1 bis 40 C-Atomen oder eine geradkettige Alkenyl- oder Alkinylgruppe mit 2 bis 40 C-Atomen oder eine verzweigte oder cyclische Alkyl-, Alkenyl-, Alkinyl-, Alkoxy- oder Thioalkoxygruppe mit 3 bis 40 C-Atomen, die jeweils mit einem oder mehreren Resten R¹ substituiert sein kann, wobei eine oder mehrere nicht benachbarte CH₂-Gruppen durch R¹C=CR¹, C=C, Si(R¹)₂, Ge(R¹)₂, Sn(R¹)₂, C=O, C=S, C=Se, C=NR¹, P(=O)(R¹), SO, SO₂, NR¹, O, S oder CONR¹ ersetzt sein können und wobei ein oder mehrere H-Atome durch D, F, Cl, Br, I, CN oder NO₂ ersetzt sein können, oder ein aromatisches oder heteroaromatisches Ringsystem mit 5 bis 60 aromatischen Ringatomen, das jeweils durch einen oder mehrere Reste R¹ substituiert sein kann, oder eine Aryloxy- oder Heteroaryloxygruppe mit 5 bis 60 aromatischen Ringatomen, die jeweils durch einen oder mehrere Reste R¹ substituiert sein kann, oder eine Kombination dieser Systeme;
• R¹ ist bei jedem Auftreten gleich oder verschieden H, D, F, Cl, Br, I, CHO, N(R²)₂, N(Ar)₂, C(=O)Ar, P(=O)(Ar)₂, S(=O)Ar, S(=O)₂Ar, CR²=CR²Ar, CN, NO₂, Si(R²)₃, B(OR²)₂, B(R²)₂, B(N(R²)₂)₂, OSO₂R², eine geradkettige Alkyl-, Alkoxy- oder Thioalkoxygruppe mit 1 bis 40 C-Atomen oder eine geradkettige Alkenyl- oder Alkinylgruppe mit 2 bis 40 C-Atomen oder eine verzweigte oder cyclische Alkyl-, Alkenyl-, Alkinyl-, Alkoxy- oder Thioalkoxygruppe mit 3 bis 40 C-Atomen, die jeweils mit einem oder mehreren Resten R² substituiert sein kann, wobei eine oder mehrere nicht benachbarte CH₂-Gruppen durch R²C=CR², C=C, Si(R²)₂, Ge(R²)₂, Sn(R²)₂, C=O, C=S, C=Se, C=NR², P(=O)(R²), SO, SO₂, NR², O, S oder CONR² ersetzt sein können und wobei ein oder mehrere H-Atome durch D, F, Cl, Br, I, CN oder NO₂ ersetzt sein können, oder ein aromatisches oder heteroaromatisches Ringsystem mit 5 bis 60 aromatischen Ringatomen, das jeweils durch einen oder mehrere Reste R² substituiert sein kann, oder eine Aryloxy- oder Heteroaryloxygruppe mit 5 bis 60 aromatischen Ringatomen, die durch einen oder mehrere Reste R² substituiert sein kann, oder eine Kombination dieser Systeme;
• Ar ist bei jedem Auftreten gleich oder verschieden ein aromatisches oder heteroaromatisches Ringsystem mit 5 bis 30 aromatischen Ringatomen, das mit einem oder mehreren nicht-aromatischen Resten R¹ substituiert sein kann; dabei können auch zwei Reste Ar, welche an dasselbe Stickstoff- oder Phosphoratom binden, durch eine Einfachbindung oder eine Brücke, ausgewählt aus B(R²), C(R²)₂, Si(R²)₂, C=O, C=NR², C=C(R²)₂, O, S, S=O, SO₂, N(R²), P(R²) und P(=O)R², miteinander verknüpft sein;
• R² ist bei jedem Auftreten gleich oder verschieden H, D oder ein aliphatischer, aromatischer und/oder heteroaromatischer Kohlenwasserstoffrest mit 1 bis 20 C-Atomen, in dem auch H-Atome durch F ersetzt sein können;
• n ist 0, 1, 2, 3, 4, 5 oder 6;
• m ist 0, 1, 2 oder 3, und wobei

die organische elektronische Vorrichtung eine organische Elektrolumineszenzvorrichtung (OLED), oder eine lichtemittierende elektrochemische Zelle (LEC) darstellt.The invention therefore relates to an organic electronic device containing cathode, anode and at least one organic layer which is arranged between cathode and anode and which has at least one compound according to formula (3), formula (4), formula (5) or formula ( 6) contains,

where the following applies to the symbols and indices used:

• In each occurrence, Y is, identically or differently, a single bond or a divalent group selected from the group consisting of B(R ¹ ) ₂ , C(R ¹ ) ₂ , NR ¹ , O, S, C(=O), C( =C(R ¹ ) ₂ , S(=O), S(=O) ₂ , P(=O)(R ¹ ) ₂ , or a divalent aromatic or heteroaromatic ring system with 5 to 18 aromatic ring atoms, which with one or several radicals R ¹ can be substituted;
• R is the same or different in each occurrence D, F, Cl, Br, I, CHO, N(R ¹ ) ₂ , N(Ar) ₂ , C(=O)Ar, P(=O)(Ar) ₂ , S(=O)Ar, S(=O) ₂ Ar, CR ¹ =CR ¹ Ar, CN, NO ₂ , Si(R ¹ ) ₃ , B(OR ¹ ) ₂ , B(R ¹ ) ₂ , B( Ar) ₂ , B(N(R ¹ ) ₂ ) ₂ , OSO ₂ R ¹ , a straight-chain alkyl, alkoxy or thioalkoxy group with 1 to 40 carbon atoms or a straight-chain alkenyl or alkynyl group with 2 to 40 carbon atoms or a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy or thioalkoxy group with 3 to 40 carbon atoms, each of which can be substituted with one or more R ¹ radicals, one or more non-adjacent CH ₂ groups being represented by R ¹ C=CR ¹ , C=C, Si(R ¹ ) ₂ , Ge(R ¹ ) ₂ , Sn(R ¹ ) ₂ , C=O, C=S, C=Se, C=NR ¹ , P (=O)(R ¹ ), SO, SO ₂ , NR ¹ , O, S or CONR ¹ can be replaced and where one or more H atoms are replaced by D, F, Cl, Br, I, CN or NO ₂ can be, or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, each of which can be substituted by one or more R ¹ radicals, or an aryloxy or heteroaryloxy group with 5 to 60 aromatic ring atoms, each of which can be substituted by one or more R radicals ¹ may be substituted, or a combination of these systems;
• R ¹ is the same or different in each occurrence as H, D, F, Cl, Br, I, CHO, N(R ² ) ₂ , N(Ar) ₂ , C(=O)Ar, P(=O)(Ar ) ₂ , S(=O)Ar, S(=O) ₂ Ar, CR ² =CR ² Ar, CN, NO ₂ , Si(R ² ) ₃ , B(OR ² ) ₂ , B(R ² ) ₂ , B(N(R ² ) ₂ ) ₂ , OSO ₂ R ² , a straight-chain alkyl, alkoxy or thioalkoxy group with 1 to 40 carbon atoms or a straight-chain alkenyl or alkynyl group with 2 to 40 carbon atoms or a branched one or cyclic alkyl, alkenyl, alkynyl, alkoxy or thioalkoxy group with 3 to 40 C atoms, each of which can be substituted with one or more R ² radicals, where one or more non-adjacent CH ₂ groups are replaced by R ² C =CR ² , C=C, Si(R ² ) ₂ , Ge(R ² ) ₂ , Sn(R ² ) ₂ , C=O, C=S, C=Se, C=NR ² , P(=O )(R ² ), SO, SO ₂ , NR ² , O, S or CONR ² can be replaced and one or more H atoms can be replaced by D, F, Cl, Br, I, CN or NO ₂ , or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, each of which may be substituted by one or more R ² radicals, or an aryloxy or heteroaryloxy group with 5 to 60 aromatic ring atoms, which may be substituted by one or more R ² radicals , or a combination of these systems;
• In each occurrence, Ar is, identically or differently, an aromatic or heteroaromatic ring system with 5 to 30 aromatic ring atoms, which may be substituted with one or more non-aromatic radicals R ¹ ; Two Ar residues, which bind to the same nitrogen or phosphorus atom, can also be formed through a single bond or a bridge, selected from B(R ² ), C(R ² ) ₂ , Si(R ² ) ₂ , C=O, C =NR ² , C=C(R ² ) ₂ , O, S, S=O, SO ₂ , N(R ² ), P(R ² ) and P(=O)R ² , be linked together;
• In each occurrence, R ² is identical or different H, D or an aliphatic, aromatic and/or heteroaromatic hydrocarbon radical with 1 to 20 carbon atoms, in which H atoms can also be replaced by F;
• n is 0, 1, 2, 3, 4, 5 or 6;
• m is 0, 1, 2 or 3, and where

the organic electronic device represents an organic electroluminescence device (OLED), or a light-emitting electrochemical cell (LEC).

For the purposes of the present invention, an organic electronic device is understood to mean a device which contains anode and cathode and at least one layer arranged between the anode and cathode, this layer containing at least one organic or organometallic compound. However, it is not necessary that the device contains only organic layers. One or more layers can also be present which contain inorganic materials or consist entirely of inorganic materials. Likewise, the anode and cathode can consist of or contain purely inorganic materials.

The organic electronic device is in particular selected from the group consisting of organic electroluminescence devices (OLEDs) or light-emitting electrochemical cells (LECs), but in particular organic electroluminescence devices (OLEDs). Disclosed herein, but not claimed, is an organic electronic device selected from organic laser diodes (O-lasers) and organic plasmon emitting devices, organic integrated circuits (O-ICs), organic field effect transistors (O-FETs), organic thin film transistors (O-TFTs), organic light-emitting transistors (O-LETs), organic solar cells (O-SCs), organic optical detectors, organic photoreceptors, organic field quench devices (O-FQDs)" (D. M. Koller et al., Nature Photonics 2008, 1-4).

An aryl group in the sense of this invention contains 6 to 60 carbon atoms; For the purposes of this invention, a heteroaryl group contains 2 to 60 carbon atoms and at least 1 heteroatom, with the proviso that the sum of carbon atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, O and/or S. An aryl group or heteroaryl group is either a simple aromatic cycle, i.e. benzene, or a simple heteroaromatic cycle, for example pyridine, pyrimidine, thiophene, etc., or a fused aryl or heteroaryl group, for example naphthalene, anthracene, pyrene, quinoline, isoquinoline, etc., understood.

An aromatic ring system in the sense of this invention contains 6 to 60 carbon atoms in the ring system. A heteroaromatic ring system in the sense of this invention contains 2 to 60 carbon atoms and at least one heteroatom in the ring system, with the proviso that the sum of carbon atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, O and/or S. An aromatic or heteroaromatic ring system in the context of this invention is to be understood as meaning a system which does not necessarily only contain aryl or heteroaryl groups, but also contains several aryl or heteroaryl groups a short, non-aromatic unit (preferably less than 10% of the atoms other than H), such as B. an sp ³ -hybridized C, N or O atom, can be interrupted. For example, systems such as 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether, stilbene, benzophenone, etc. should also be understood as aromatic ring systems within the meaning of this invention. Likewise, an aromatic or heteroaromatic ring system is understood to mean systems in which several aryl or heteroaryl groups are linked to one another by single bonds, for example biphenyl, terphenyl or bipyridine.

In the context of the present invention, a C ₁ to C ₄₀ alkyl group, in which individual H atoms or CH ₂ groups can also be substituted by the above-mentioned groups, is particularly preferably the radicals methyl, ethyl, n-propyl, i-Propyl, n-Butyl, i-Butyl, s-Butyl, t-Butyl, 2-Methylbutyl, n-Pentyl, s-Pentyl, Cyclopentyl, n-Hexyl, Cyclohexyl, n-Heptyl, Cycloheptyl, n-Octyl, Cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl and 2,2,2-trifluoroethyl are understood. For the purposes of this invention, an alkenyl group is understood to mean, in particular, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl and cyclooctenyl. For the purposes of this invention, an alkynyl group is understood to mean, in particular, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl or octynyl. A C ₁ to C ₄₀ alkoxy group is particularly preferably understood to mean methoxy, trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy or 2-methylbutoxy. Under an aromatic cal or heteroaromatic ring system with 5 - 60 aromatic ring atoms, which can also be substituted with the above-mentioned radicals R and which can be linked via any positions on the aromatic or heteroaromatic, are understood in particular to be groups that are derived from benzene, naphthalene, Anthracene, phenanthrene, benzanthracene, pyrene, chrysene, perylene, fluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, biphenylene, terphenyl, terphenylene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indenofluorene, truxene, isotruxene, spirotruxene , spiroisotruxene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7 -quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthimidazole, phenanthrimidazole, pyridimidazole, pyrazinimidazole, quinoxalinimidazole, oxazole, benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, 1,2-thiazole , 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, 1,5-diazaanthracene, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4 ,5-diazapyrene, 4,5,9,10-tetraazaperylene, pyrazine, phenazine, phenoxazine, phenothiazine, fluorubin, naphthyridine, azacarbazole, benzocarboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole , 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1 ,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine , 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine and benzothiadiazole.

The compounds according to formula (3), formula (4), formula (5) or formula (6) preferably have a glass transition temperature T _G of greater than 70 ° C, particularly preferably greater than 100 ° C, very particularly preferably greater than 110°C.

Furthermore, in the compounds according to formula (4) and formula (6), R ¹ is preferably hydrogen. The compounds of formula (3) are very particularly preferred.

In a preferred embodiment of the invention, the index n in compounds of the formula (3) and (4) is 0, 1 or 2, particularly preferably 0 or 1, very particularly preferably 0.

In a further preferred embodiment of the invention, the index m in compounds of the formula (5) and (6) is 1 or 2, particularly preferably 1.

In a preferred embodiment of the invention, R in the compounds of the formulas (3) to (6) is identical or different in each occurrence for F, N(R ¹ ) ₂ , N(Ar) ₂ , C(=O)Ar, P (=O)(Ar) ₂ , CN, NO ₂ , a straight-chain alkyl group with 1 to 10 carbon atoms or a branched or cyclic alkyl group with 3 to 10 carbon atoms, which can each be substituted with one or more radicals R ¹ , where one or more H atoms can be replaced by F or CN, or an aromatic or heteroaromatic ring system with 5 to 40 aromatic ring atoms, which can each be substituted by one or more R ¹ radicals. In a particularly preferred embodiment of the invention, R in the compounds of the formulas (3) to (6) is identical or different in each occurrence for F, CN, CF ₃ , or an aromatic or heteroaromatic ring system with 5 to 30 aromatic ring atoms, which in each case can be substituted by one or more radicals R ¹ . Particularly preferred aromatic or heteroaromatic ring systems which can form the group R are selected from the group consisting of phenyl, 2-, 3- or 4-pyridyl, pyrazinyl, 2-, 4- or 5-pyrimidinyl, 3- or 4- Pyridazinyl, ortho-, meta- or para-biphenyl, ortho-, meta- or para-terphenyl, 2-fluorenyl, 2-spirobifluorenyl, 1-naphthyl, 2-naphthyl, anthracenyl, phenylanthracenyl, 1- or 2-naphthylanthracenyl, binaphthyl , pyrenyl, fluoranthenyl, 2-, 3-, 4-, 5-, 6- or 7-benzanthracenyl, N-imidazolyl, N-benzimidazolyl, phenyl-N-benzimidazolyl, N-phenylbenzimidazolyl, phenyl-N-phenylbenzimidazolyl or combinations of these Groups which can each be substituted by one or more radicals R ¹ .

It is particularly preferred that all R radicals are chosen the same. This applies in particular to the preferred and particularly preferred radicals R listed above. This preference is based on the better synthetic accessibility of the compounds.

Particularly preferred are the structures of the formulas (3) to (6) listed above, in which n = 0 or 1, in particular n = 0, and m = 1 and in which R has the preferred or particularly preferred meaning listed above .

Preference is also given to the structures of formulas (3) to (6) listed above, in which Y is the same or different each time it occurs for a single bond or a divalent group the group consisting of C(R ¹ ) ₂ , NR ¹ and a divalent aryl or heteroaryl group with 5 to 14 aromatic ring atoms, which may be substituted with one or more R ¹ radicals. Y in formulas (3) and (4) is particularly preferably selected, identically or differently, in each occurrence from a single bond, NR ¹ or a divalent aryl or heteroaryl group with 5 to 10 aromatic ring atoms, which is substituted with one or more radicals R ¹ can be. Particularly preferably, Y in formulas (5) and (6) is the same or different for each occurrence of NR ¹ .

(1) (2)

(3) (4)

(5) (6)

(7) (8)

(9) (10)

(11) (12)

(13) (14)

(15) (16)

(17) (18)

(19) (20)

(21) (22)

(23) (24)

(25) (26)

(27) (28)

(29) (30)

(31) (32)

(33) (34)

(35) (36)

(37) (38)

(39) (40)

(41) (42)

(43) (44)

(45) (46)

#(47) #(48)

#(49) #(50)

#(51) #(52)

#(53) #(54)

#(55) #(56)

#(57) #(58)

#(59) #(60)

#(61) #(62)

#(63) #(64)

#(65) #(66)

#(67) #(68)

#(69) #(70)

#(71) #(72)

#(73) #(74)

#(75) #(76)

#(77) #(78)

(79) (80)

(81) (82)

(83) #(84) Examples of preferred compounds according to formulas (3) to (6) are the structures (1) to (84) shown below. The structures marked with # below are not according to the invention.

(1) (2)

(3) (4)

(5) (6)

(7) (8th)

(9) (10)

(11) (12)

(13) (14)

(15) (16)

(17) (18)

(19) (20)

(21) (22)

(23) (24)

(25) (26)

(27) (28)

(29) (30)

(31) (32)

(33) (34)

(35) (36)

(37) (38)

(39) (40)

(41) (42)

(43) (44)

(45) (46)

#(47) #(48)

#(49) #(50)

#(51) #(52)

#(53) #(54)

#(55) #(56)

#(57) #(58)

#(59) #(60)

#(61) #(62)

#(63) #(64)

#(65) #(66)

#(67) #(68)

#(69) #(70)

#(71) #(72)

#(73) #(74)

#(75) #(76)

#(77) #(78)

(79) (80)

(81) (82)

(83) #(84)

The synthesis of the compounds according to formulas (3) to (6) is known to those skilled in organic chemistry. In all cases, trihalo-heptaazaphenalene or a corresponding phenalene derivative with fewer nitrogen atoms can serve as the starting compound. Trichlorheptaazaphenalene is particularly suitable. This can be obtained by direct chlorination of the corresponding acid, for example according to EP 1 854 797 A1 . This can also be obtained by Sandmeyer reaction, i.e. by diazotization, of triaminoheptaazaphenalene, which in turn is directly accessible from melamine (e.g. according to H. May, J. Applied Chemistry 1959, 9, 340-344). The chlorine substituents can then be exchanged for other nucleophiles, for example F or CN, by nucleophilic aromatic substitution, in particular with activation by a Lewis acid. The introduction of other groups, for example substituted amino groups, is also possible. Furthermore, the introduction of aromatic substituents by Friedel-Crafts reaction is possible. The introduction of aromatic or heteroaromatic substituents is also possible by reaction of trichloroheptaazaphenalene with organometallic derivatives of aromatic or heteroaromatic compounds, in particular with organolithium compounds or Grignard compounds. Furthermore, palladium-catalyzed coupling reactions, in particular with boronic acid derivatives (Suzuki coupling) or organozinc compounds (Negishi coupling), are possible to introduce aromatic substituents. Diarylamino groups can be introduced by palladium-catalyzed Hartwig–Buchwald coupling. The halogen function can be converted into an electrophilic group by transmetalation with organolithium compounds or Grignard compounds, which is then reacted with a variety of electrophiles, such as. B. aryl-boron halides, aldehydes, ketones, nitriles, esters, halogen esters, carbon dioxide, arylphosphine halides, halosulfinic acids, haloarylsulfonic acids, etc., can be coupled. The trinitro compound is accessible from triaminoheptaazaphenalens by oxidation. Asymmetrically substituted compounds can each be obtained by adjusting the stoichiometry. These reactions are listed schematically in Scheme 1 below.

Furthermore, the corresponding triamino compound can be used from the starting compound. The amino groups can be converted into the nitro groups through oxidation. Furthermore, the amino groups can be substituted, for example by the Hartwig-Buchwald reaction.

Cyclic compounds of the formula (5) with Y = NH are accessible by heating 2,6,10-triaminoheptaazaphenals to 450 to 600 ° C for 15 to 60 minutes (e.g. according to SU 1 747 448 A1 ). These can be further functionalized as described above for the non-cyclic compounds.

The compounds of formulas (3) to (6) described above, in particular compounds in which at least one group R represents a reactive leaving group, such as bromine, iodine, triflate, tosylate, boronic acid or boronic acid ester, can also be used as monomers to produce corresponding Oligomers, polymers or as the core of dendrimers are used, these oligomers, polymers and dendrimers in turn being suitable for use in organic electronic devices, in particular in organic electroluminescent devices. The oligomerization or polymerization preferably takes place via the halogen functionality or the boronic acid functionality. For the purposes of this invention, an oligomer is understood to mean a compound which has approximately 3 to 9 repeating units. A polymer in the context of this invention has approximately 10 or more repeating units.

The invention therefore further provides organic electronic devices, in particular organic electroluminescent devices, containing at least one oligomer, polymer or dendrimer which contains one or more compounds according to formula (3) to (6), where one or more radicals R bonds of the compound according to formula (3) to (6) represent the polymer, oligomer or dendrimer. The polymers, oligomers or dendrimers can be conjugated, partially conjugated or non-conjugated. The oligomers or polymers can be linear or branched. In the linearly linked structures, the units according to formulas (3) to (6) can be linked directly to one another or they can be linked via a divalent group, for example via a substituted or unsubstituted alkylene group, via a hetero atom or via a bivalent aromatic or heteroaromatic group. In branched structures, for example, three or more units according to formulas (3) to (6) can be linked via a trivalent or higher-valent group, for example via a trivalent or higher-valent aromatic or heteroaromatic group, to form a branched oligomer or polymer. Furthermore, the units according to formula (3) to (6) are particularly suitable as branching points in oligomers, polymers and dendrimers, since the trichlorine-substituted units are easily accessible.

To produce the oligomers or polymers, the corresponding monomers are homopolymerized or copolymerized with other monomers. Suitable and preferred comonomers are selected from fluorenes (e.g. according to EP 842 208 A1 or WO 00/22 026 A1 ), spirobifluorenes (e.g. according to EP 707 020 A2 , EP 894 107 A1 or WO 06/061 181 A1 ), para-phenylenes (e.g. according to WO 92/18 552 A1 ), carbazoles (e.g. according to WO 04/070 772 A2 or WO 04/113 468 A1 ), thiophenes (e.g. according to EP 1 028 136 A2 ), dihydrophenanthrenes (e.g. according to WO 2005/014 689 A2 ), cis- and trans-indenofluorenes (e.g. according to WO 2004/041 901 A1 or WO 2004/113 412 A2 ), ketones (e.g. according to WO 2005/040 302 A1), phenanthrenes (e.g. according to WO 2005/104 264 A1 or WO 2007/017 066 A1) or several of these units. The polymers, oligomers and dendrimers usually contain further units, for example emitting (fluorescent or phosphorescent) units, such as. B. vinyl triarylamines (e.g. according to WO 2007/068 325 A1 ) or phosphorescent metal complexes (e.g. according to WO 2006/003 000 A1 ), and/or cargo transport units. The repeating units according to the invention are particularly suitable as charge transport units for electrons.

A further subject of the invention is the use of compounds according to formula (3), (4), (5) or (6) or corresponding oligomers, polymers or dendrimers in organic electronic devices, in particular in organic electroluminescent devices.

The organic electroluminescent device contains anode, cathode and at least one emitting layer, wherein at least one organic layer, which may be the emitting layer or another layer, at least one compound according to formula (3) to (6) or a corresponding oligomer, polymer or dendrimer contains.

In addition to the cathode, anode and the emitting layer, the organic electroluminescent device can contain further layers. These are, for example, selected from one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, electron blocking layers, exciton blocking layers, charge generation layers and/or organic or inorganic p/n junctions. Furthermore, the layers, in particular the charge transport layers, can also be doped. Doping the layers can be advantageous for improved charge transport. However, it should be noted that each of these layers does not necessarily have to be present and the choice of layers always depends on the compounds used and in particular on the fact whether it is a fluorescent or phosphorescent electroluminescent device.

In one embodiment of the invention, the organic electroluminescent device contains a plurality of emitting layers, wherein at least one organic layer, which may be an emitting layer or another layer, contains at least one compound according to one of the formulas (3) to (6). Particularly preferably, these emission layers have a total of several emission maxima between 380 nm and 750 nm, so that overall white emission results, that is, various emitting compounds are used in the emitting layers which can fluoresce or phosphorescent and which emit blue and yellow, orange or red light . Particularly preferred are three-layer systems, i.e. systems with three emitting layers, where at least one of these layers contains at least one compound according to one of the formulas (3) to (6) and where the three layers show blue, green and orange or red emission (for the basic Structure see e.g. WO 2005/011 013 A1 ). Emitters that have broadband emission bands and therefore show white emission are also suitable for white emissions.

In a preferred embodiment of the invention, the compounds according to formulas (3) to (6) are used as hole injection or hole transport material. This applies in particular if at least one substituent R, preferably at least two substituents R, particularly preferably all three substituents R represent an electron-deficient group. In contrast to triarylamine derivatives, which are usually used in the hole injection or hole transport layer and in which the hole transport occurs via the HOMO (“highest occupied molecular orbital”) of the corresponding compound In the case of compounds of the formulas (3) to (6), the hole transport does not take place via the HOMO, but rather via the LUMO (“lowest unoccupied molecular orbital”). Particularly preferred substituents R are then selected from the group consisting of CN, F, NO ₂ , CF ₃ and substituted or unsubstituted electron-poor heterocycles. The electron-poor heterocycles are selected from pyridine, pyrazine, pyrimidine, pyridazine, triazine, pyrrole, imidazole, triazole and benzimidazole. Since the LUMO of these compounds is the same or even lower than the hexaazatriphenylene derivatives used as hole injection materials according to the prior art, the compounds according to formulas (3) to (6) are just as suitable or better than the materials according to the state of the art as hole injection or hole transport materials. A hole injection material in the sense of this invention is to be understood as meaning a compound which is used in a hole injection layer. A hole injection layer in the sense of this invention is a layer which is directly adjacent to the anode. The hole injection layer in the structure of the organic electroluminescence device is usually followed by a hole transport layer, so that the hole injection layer lies between the anode and a hole transport layer. A hole transport layer in the sense of the present invention is a layer which lies between a hole injection layer and the emitting layer.

In a preferred embodiment of the invention, the electroluminescence device according to the invention comprises a structure containing in this order: anode - hole injection layer containing at least one compound according to one of the formulas (3) to (6) - hole transport layer, preferably containing at least one triarylamine derivative - emitting layer - cathode. It is also possible in this structure to use two or more hole transport layers, all of which preferably contain at least one triarylamine derivative. A further preferred structure of the electroluminescent device contains in this order: anode - hole injection layer, preferably containing at least one triarylamine derivative - hole transport layer, containing at least one compound according to one of the formulas (3) to (6) - hole transport layer, preferably containing at least one triarylamine derivative - emitting layer - Cathode. It is also possible in this structure that a further hole transport layer, preferably containing at least one triarylamine derivative, is introduced between the hole injection layer and the layer containing the compound according to one of the formulas (3) to (6) and / or that instead of a hole transport layer, which is preferred contains a triarylamine derivative, two or more hole transport layers, each of which preferably contains at least one triarylamine derivative, are used between the layer containing the compound according to one of the formulas (3) to (6) and the emitting layer. In addition, these devices can also contain one or more of the additional layers listed above, for example electron transport layers, etc.

In yet another embodiment of the invention, the compounds according to formulas (3) to (6) are used as electron transport material or as hole blocking material in an electron transport layer or a hole blocking layer. A hole blocking layer in the context of this invention is a layer that lies between an emitting layer and an electron transport layer and directly adjoins the emitting layer. Here it is preferred if the substituents R, the same or different, represent an aromatic or heteroaromatic ring system in each occurrence, which are preferably selected from the groups mentioned above. Furthermore, it may be preferred if the compound is doped with electron donor compounds. This is particularly true for use in an electron transport layer. Suitable dopants are alkali metals or alkali metal complexes or compounds, in particular lithium compounds, for example lithium quinolinate.

In yet another embodiment of the invention, the compounds according to formulas (3) to (6) are used as charge generation material in a charge generation layer.

In the above-mentioned functions, i.e. in particular as a hole injection or transport material, as an electron transport material or as a charge generation material, the materials are also suitable for other organic electronic devices such as those mentioned above.

Metals with a low work function, metal alloys or multilayer structures made of different metals are preferred as the cathode of the electronic device according to the invention, such as alkaline earth metals, alkali metals, main group metals or lanthanoids (e.g. Ca, Ba, Mg, Al, In, Mg, Yb, Sm , Etc.). In the case of multi-layer structures, in addition to the metals mentioned, other metals can also be used that have a relatively high work function, such as. B. Ag, in which case combinations of metals, such as Ca/Ag or Ba/Ag, are generally used. Also preferred are metal alloys, in particular alloys made of an alkali metal or alkaline earth metal and silver, particularly preferably an alloy of Mg and Ag. It may also be preferred to introduce a thin intermediate layer of a material with a high dielectric constant between a metallic cathode and the organic semiconductor. For example, alkali metal or alkaline earth metal fluorides, but also the corresponding oxides or carbonates come into consideration for this (e.g. LiF, Li ₂ O, CsF, Cs ₂ CO ₃ , BaF ₂ , MgO, NaF, etc.). The layer thickness of this intermediate layer is preferably between 0.5 and 5 nm.

Materials with a high work function are preferred as the anode of the electronic device according to the invention. The anode preferably has a work function greater than 4.5 eV vs. vacuum. On the one hand, metals with a high redox potential are suitable for this, such as Ag, Pt or Au. On the other hand, metal/metal oxide electrodes (e.g. Al/Ni/NiO _x , Al/PtO _x ) may also be preferred. For some applications, at least one of the electrodes must be transparent to enable either the irradiation of the organic material (O-SC) or the extraction of light (OLED/PLED, O-laser). A preferred construction uses a transparent anode. Preferred anode materials here are conductive mixed metal oxides. Indium-tin oxide (ITO) or indium-zinc oxide (IZO) are particularly preferred. Conductive, doped organic materials, in particular conductive doped polymers, are also preferred.

The device is structured accordingly (depending on the application), contacted and finally hermetically sealed, since the service life of such devices is drastically shortened in the presence of water and/or air.

In general, all other materials such as those used in organic electroluminescent devices according to the prior art can also be used in combination with the compounds according to formulas (3) to (6). The emitting layer can contain fluorescent and/or phosphorescent dopants, preferably in combination with a matrix material (host material).

Suitable fluorescent dopants are selected from the class of monostyrylamines, distyrylamines, tristyrylamines, tetrastyrylamines, styrylphosphines, styryl ethers and arylamines. A monostyrylamine is understood to mean a compound that contains a substituted or unsubstituted styryl group and at least one, preferably aromatic, amine. A distyrylamine is understood to mean a compound that contains two substituted or unsubstituted styryl groups and at least one, preferably aromatic, amine. A tristyrylamine is understood to mean a compound that contains three substituted or unsubstituted styryl groups and at least one, preferably aromatic, amine. A tetrastyrylamine is understood to mean a compound that contains four substituted or unsubstituted styryl groups and at least one, preferably aromatic, amine. The styryl groups are particularly preferably stilbenes, which can also be further substituted. Corresponding phosphines and ethers are defined analogously to amines. For the purposes of this invention, an arylamine or an aromatic amine is understood to mean a compound which contains three substituted or unsubstituted aromatic or heteroaromatic ring systems bound directly to the nitrogen. At least one of these aromatic or heteroaromatic ring systems is preferably a fused ring system, particularly preferably with at least 14 aromatic ring atoms. Preferred examples of this are aromatic anthracene amines, aromatic anthracene diamines, aromatic pyrene amines, aromatic pyrene diamines, aromatic chrysene amines or aromatic chrysene diamines. An aromatic anthracenamine is understood to mean a compound in which a diarylamino group is bonded directly to an anthracene group, preferably in the 9-position. An aromatic anthracene diamine is understood to mean a compound in which two diarylamino groups are bonded directly to an anthracene group, preferably in the 9,10 position. Aromatic pyrenamines, pyrenediamines, chrysenamines and chrysenediamines are defined analogously, with the diarylamino groups on the pyrene preferably being bound in the 1-position or in the 1,6-position. Further preferred dopants are selected from indenofluorenamines or diamines, for example according to WO 2006/122 630 A1 , benzoindenofluorenamines or diamines, for example according to WO 2008/006 449 A1 , and dibenzoindenofluorenamines or diamines, for example according to WO 2007/140 847 A1 . Examples of dopants from the class of styrylamines are substituted or unsubstituted tristilbenamines or the dopants contained in WO 2006/000 388 A1 , WO 2006/058 737 A1 , WO 2006/000 389 A1 , WO 2007/065 549 A1 and WO 2007 / 115 610 A1 are described. Also preferred are those in DE 10 2008 035 413 A1 disclosed condensed hydrocarbons.

Other suitable fluorescent dopants are the structures shown in the following table and those in JP 2006 - 001 973 A , WO 2004/047 499 A1 , WO 2006/098 080 A1 , WO 2007/065 678 A1 , US 2005 / 0 260 442 A1 and WO 2004/092 111 A1 disclosed derivatives of these structures.

Suitable host materials for the fluorescent emitters are selected from the classes of oligoarylenes (e.g. 2,2',7,7'-tetraphenylspirobifluorene according to EP 0 676 461 A2 or dinaphthylanthracene), in particular the oligoarylenes containing fused aromatic groups, the oligoarylene vinylenes (e.g. DPVBi or Spiro-DPVBi according to EP 0 676 461 A2 ), the polypodal metal complexes (e.g. according to WO 2004/081 017 A1 ), the hole-conducting connections (e.g. according to WO 2004/058 911 A2 ), the electron-conducting compounds, in particular ketones, phosphine oxides, sulfoxides, etc. (e.g. according to WO 2005/084 081 A1 and WO 2005/084 082 A1 ), the atropisomers (e.g. according to WO 2006/048 268 A1 ), the boronic acid derivatives (e.g. according to WO 2006/117 052 A1 ), the benzanthracenes (e.g. according to WO 2008 / 145 239 A2 ) or the benzophenanthrenes (e.g. according to DE 10 2009 005 746 A1 ). Particularly preferred host materials are selected from the classes of oligoarylenes, containing naphthalene, anthracene, benzanthracene, benzophenanthrene and/or pyrene or atropisomers of these compounds, the oligoarylene vinylenes, the ketones, the phosphine oxides and the sulfoxides. Very particularly preferred host materials are selected from the classes of oligoarylenes containing anthracene, benzanthracene, benzophenanthrene and/or pyrene or atropisomers of these compounds. For the purposes of this invention, an oligoarylene is to be understood as meaning a compound in which at least three aryl or arylene groups are bonded to one another.

Suitable host materials are, for example, the materials shown in the following table, as well as derivatives of these materials, as shown in WO 2004/018 587 A1 , WO 2008/006 449 A1 , US 5,935,721 A , US 2005 / 0 181 232 A1 , JP 2000/273 056 A2 , EP 681 019 A2 , US 2004 / 0 247 937 A1 and US 2005 / 0 211 958 A1 be revealed.

Particularly suitable phosphorescent compounds are compounds which, when stimulated appropriately, emit light, preferably in the visible range, and also contain at least one atom with an atomic number greater than 20, preferably greater than 38 and less than 84, particularly preferably greater than 56 and less than 80. Compounds which contain copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium are preferably used as phosphorescence emitters, in particular compounds which contain iridium or platinum. For the purposes of the present application, all luminescent metal complexes that contain the above-mentioned metal are referred to as phosphorescent compounds.

Examples of suitable phosphorescent emitters can be found in the applications WO 00/70 655 A2 , WO 01/41 512 A1 , WO 02/02 714 A2 , WO 02/15 645 A1 , EP 1 191 613 A2 , EP 1 191 612 A2 , EP 1 191 614 A2 , WO 2004/081 017 A1 , WO 2005/033 244 A1 , WO 2005/042 550 A1 , WO 2005/113 563 A1 , WO 2006/008 069 A1 , WO 2006/061 182 A1 , WO 2006/081 973 A1 and DE 10 2008 027 005 A1 be removed. In general, all phosphorescent complexes such as those used in the prior art for phosphorescent OLEDs are suitable.

Suitable matrix materials for the phosphorescent emitter are selected from the group consisting of aromatic ketones, phosphine oxides, sulfoxides and sulfones, e.g. B. according to WO 2004/013 080 A1 , WO 2004/093 207 A2 , WO 2006/005 627 A1 or DE 10 2008 033 943 A1 , triarylamines, carbazole derivatives, e.g. B. CBP (N,N-biscarbazolylbiphenyl) or the in WO 2005/039 246 A1 , US 2005 / 0 069 729 A1 , JP 2004 - 288 381 A , EP 1 205 527 A1 or WO 2008/086 851 A1 disclosed carbazole derivatives, cis- and trans-indolocarbazole derivatives, e.g. B. according to WO 2007/063 754 A1 or WO 2008/056 746 A1 , azacarbazoles, e.g. B. according to EP 1617710 , EP 1617711 , EP 1731584 , JP 2005/347160 , bipolar matrix materials, e.g. B. according to WO 2007/137 725 A1 , silanes, e.g. B. according to WO 2005/111 172 A2 , azaborolene or boron esters, e.g. B. according to WO 2006/117 052 A1 , triazine derivatives, e.g. B. according to DE 10 2008 036 982 A1 , WO 2007/063 754 A1 or WO 2008/056 746 A1 , or zinc complexes, e.g. B. according to the undisclosed application DE 10 2007 053 771 A1 .

Suitable charge transport materials, such as those which can be used in the hole injection or hole transport layer or in the electron transport layer of the organic electroluminescent device according to the invention, are, for example, in addition to the materials according to the invention, those in Y. Shirota et al., Chem. Rev. 2007, 107(4), 953-1010 disclosed compounds or other materials as used in these layers according to the prior art.

Examples of preferred hole transport materials that can be used in a hole transport or hole injection layer in the electroluminescent device according to the invention are indenofluorenamines and derivatives (e.g. according to WO 2006/122 630 A1 or WO 2006/100 896 A1 ), in the EP 1 661 888 A1 disclosed amine derivatives, hexaazatriphenylene derivatives (e.g. according to WO 01/049 806 A1 ), amine derivatives with condensed aromatics (e.g. according to US 5,061,569 A ), in the WO 95/09 147 A1 disclosed amine derivatives, monobenzoindenofluorenamines (e.g. according to WO 2008/006 449 A1 ) or dibenzoindenofluorenamines (e.g. according to WO 2007/140 847 A1 ). Further suitable hole transport and hole injection materials are derivatives of the above-mentioned compounds, as described in JP 2001 - 226331 A , EP 0 676 461 A2 , EP 650 955 A1 , WO 01/049 806 A1 , US 4,780,536 A , WO 98/30 071 A1 , EP 0 891 121 A1 , EP 1 661 888 A1 , JP 2006 - 253445 A , EP 650 955 A1 , WO 2006/073 054 A1 and US 5,061,569 A be revealed.

Suitable hole transport or hole injection materials are also, for example, the materials listed in the following table.

Suitable electron transport or electron injection materials that can be used in the electroluminescent device according to the invention include, for example, the materials listed in the following table. Further suitable electron transport and electron injection materials are derivatives of the compounds shown above, as in JP 2000 - 053 957 A , WO 2003/060 956 A2 , WO 2004/028 217 A1 and WO 2004/080 975 A1 be revealed.

Furthermore preferred is an organic electroluminescence device, characterized in that one or more layers are coated using a sublimation process. The materials are vapor-deposited in vacuum sublimation systems at an initial pressure of less than 10 ^-5 mbar, preferably less than 10 ^-6 mbar. However, it should be noted that the initial pressure can also be even lower, for example less than 10 ^-7 mbar.

An organic electroluminescence device is also preferred, characterized in that one or more layers are coated using the OVPD (Organic Vapor Phase Deposition) process or with the aid of carrier gas sublimation. The materials are applied at a pressure between 10 ^-5 mbar and 1 bar. A special case of this process is the OVJP (Organic Vapor Jet Printing) process, in which the materials are applied directly through a nozzle and structured in this way (e.g. MS Arnold et al., Appl. Phys. Lett. 2008, 92, 053301 ).

Further preferred is an organic electroluminescence device, characterized in that one or more layers of solution, such as. B. by spin coating, or with any printing process, such as. B. screen printing, flexographic printing or offset printing, but particularly preferably LITI (Light Induced Thermal Imaging, thermal transfer printing) or ink-jet printing (inkjet printing). Soluble compounds are necessary for this. High solubility can be achieved through appropriate substitution of the compounds. Not only solutions made from individual materials can be applied, but also solutions that contain several compounds, for example matrix material and dopant.

It is also possible to combine several of these processes and, for example, to vapor deposit one or more layers and to apply one or more further layers from solution.

The above-mentioned methods are a further subject of the present invention.

1. 1. Die Verbindungen der Formeln (3) bis (6) weisen eine hohe thermische Stabilität auf und lassen sich unzersetzt sublimieren.
2. 2. Die Verbindungen gemäß den Formeln (3) bis (6), insbesondere Verbindungen gemäß Formel (3), welche mit elektronenarmen Substituenten, insbesondere F, CN und/oder elektronenarmen Heterocyclen, substituiert sind, eignen sich sehr gut als Lochinjektionsmaterial bzw. als Lochtransportmaterial für die Verwendung in einer Lochinjektionsschicht bzw. in einer Lochtransportschicht und führen bei dieser Verwendung zu hohen Effizienzen, insbesondere zu hohen Leistungseffizienzen, und langen Lebensdauern.
3. 3. Die Verbindungen gemäß den Formeln (3) bis (6), insbesondere solche, welche mit aromatischen oder heteroaromatischen Gruppen substituiert sind, eignen sich sehr gut als Elektronentransportmaterial oder als Lochblockiermaterial für die Verwendung in einer Elektronentransportschicht bzw. in einer Lochblockierschicht und führen bei dieser Verwendung zu hohen Effizienzen, insbesondere zu hohen Leistungseffizienzen, und langen Lebensdauern.
4. 4. Die Verbindungen gemäß den Formeln (3) bis (6) weisen eine sehr hohe Photostabilität auf, zersetzen sich also nicht unter der Einwirkung von Licht, und sind daher sehr gut für den Einsatz sowohl in organischen Elektrolumineszenzvorrichtungen wie auch in organischen Solarzellen geeignet.

When used in organic electroluminescent devices, the compounds according to the invention have the following surprising advantages over the prior art:

1. 1. The compounds of formulas (3) to (6) have high thermal stability and can be sublimated without decomposition.
2. 2. The compounds according to formulas (3) to (6), in particular compounds according to formula (3), which are substituted with electron-poor substituents, in particular F, CN and / or electron-poor heterocycles, are very suitable as hole injection material or as Hole transport material for use in a hole injection layer or in a hole transport layer and, in this use, lead to high efficiencies, in particular high power efficiencies, and long service lives.
3. 3. The compounds according to formulas (3) to (6), in particular those which are substituted with aromatic or heteroaromatic groups, are very suitable as electron transport material or as hole blocking material for use in an electron transport layer or in a hole blocking layer and lead to This use leads to high efficiencies, especially high power efficiencies, and long service lives.
4. 4. The compounds according to formulas (3) to (6) have a very high photostability, i.e. do not decompose under the influence of light, and are therefore very suitable for use both in organic electroluminescent devices and in organic solar cells.

The invention is described in more detail by the following examples, without intending to limit it.

Examples:

Unless otherwise stated, the following syntheses are carried out under an inert gas atmosphere in dried solvents. The solvents and reagents can be obtained from Fir ALDRICH or ABCR can be obtained. The precursor trichlorheptaazaphenalen can be used according to EP 1 854 797 A1 getting produced.

Triphenylheptaazaphenalene and trimesitylheptaazaphenalene can be used according to H. Schröder et al., J. Org. Chem. 1962, 27, 4262-4266 getting produced.

Example 1: Synthesis of Tricyanoheptaazaphenalen (HIM-1)

50 g (181 mmol) Trichlorheptaazaphenalen und 53.45 g (597 mmol, 3.3 Äquivalente) Kupfer(I)cyanid werden in 750 mL DMF suspendiert und unter Argon für 60 h auf 130 °C erhitzt. Nach Abkühlen auf Raumtemperatur wird die Reaktionsmischung in 1000 mL konzentrierte Ammoniaklösung gegeben und 4 h an der Luft kräftig gerührt. Der dabei ausfallende organische Niederschlag wird abgesaugt und mit kaltem Ethanol gewaschen. Der Rückstand wird mit Acetonitril soxhletiert, der auskristallisierte Niederschlag wird abgesaugt, mit wenig kaltem Acetonitril gewaschen und im Vakuum getrocknet. Ausbeute: 39.1 g (157 mmol), 87 % der Theorie; Reinheit ca. 99.8 % (HPLC).

50 g (181 mmol) of trichlorheptaazaphenalen and 53.45 g (597 mmol, 3.3 equivalents) of copper(I) cyanide are suspended in 750 mL of DMF and heated to 130 °C under argon for 60 h. After cooling to room temperature, the reaction mixture is added to 1000 mL of concentrated ammonia solution and stirred vigorously in air for 4 h. The resulting organic precipitate is filtered off with suction and washed with cold ethanol. The residue is soxhletated with acetonitrile, the crystallized precipitate is filtered off with suction, washed with a little cold acetonitrile and dried in vacuo. Yield: 39.1 g (157 mmol), 87% of theory; Purity approx. 99.8% (HPLC).

Example 2: Fabrication and characterization of organic electroluminescent devices

The production of OLEDs according to the invention takes place according to a general process WO 2004/058 911 A2 , which is adapted to the circumstances described here (layer thickness variation, materials used).

The following examples 3 to 8 present the results of various OLEDs. Glass plates coated with structured ITO (indium tin oxide) form the substrates of the OLEDs. For improved processing, 20 nm PEDOT (spin-coated from water; obtained from H. C. Starck, Goslar, Germany; poly(3,4-ethylenedioxy-2,5-thiophene)) is applied to the substrate. The OLEDs consist of the following layer sequence: substrate / PEDOT 20 nm / hole injection layer (HIL) 5 nm / hole transport layer (HTL-1) 20 nm / hole transport layer (HTL-2) 20 nm / emission layer (EML) 30 nm / electron transport layer (ETL) 20 nm and finally a cathode.

The materials except for PEDOT are thermally vapor deposited in a vacuum chamber. The emission layer always consists of a matrix material (host) and a dopant (dopant), which is added to the host by co-evaporation. In Examples 3 to 8 listed below, the matrix material used is the compound H1, which is doped with 10% D1 in each case. These OLEDs show green emission. The HTM-1 compound is used as the hole transport material in the HTL-1. NPB is used as the hole transport material in the HTL-2. The cathode is formed by a 1 nm thick LiF layer and a 100 nm thick Al layer deposited on top. Table 1 shows the chemical structures of the materials used to build the OLEDs.

These OLEDs are characterized as standard; For this purpose, the electroluminescence spectra, the efficiency (measured in cd/A), the power efficiency (measured in Im/W) depending on the brightness, calculated from current-voltage-brightness characteristics (IUL characteristics), and the service life are determined. The lifespan is defined as the time after which the initial brightness of 25,000 cd/m ² has fallen to half. The threshold voltage is defined as the voltage at which the OLED achieves a brightness of 1 cd/m ² .

Table 2 summarizes the results of some OLEDs (Examples 3 to 8). According to the invention, HIM-1 (tricyanoheptaazaphenalene, from Example 1) or HIM-2 (hexacyanohexaazatriphenylene, according to the prior art) are used as hole injection material in the hole injection layer (HIL). Compared to the prior art, OLEDs containing HIM-1 in the hole injection layer are characterized by improved efficiency, in particular improved power efficiency, and service life compared to HIM-2 according to the state of the art. The starting voltage and color coordinates when using HIM-1 according to the invention are very similar to those when using HIM-2 according to the prior art.

HTM-1 NPB

HIM-1 HIM-2 (Stand der Technik)

H1 D1

ETM-1 ETM-2

AlQ₃ (Stand der Technik) Tabelle 2 Bsp. HIL ETL Einsatzspannung Spannung für 1000 cd/m² Effizienz bei 1000 cd/m² Leistungseffizienz bei 1000 cd/m² CIE x/y bei 1000 cd/m² Lebensdauer für 25000 cd/m² 3 HIM-1 AlQ₃ 2.7 V 4.8 V 18.9 cd/A 12.4 Im/W 0.34/0.63 410 h 4 (Vergl.) HIM-2 AlQ₃ 2.8 V 5.0 V 17.1 cd/A 10.7 Im/W 0.34/0.62 355 h 5 HIM-1 ETM-1 2.8 V 5.0 V 19.2 cd/A 12.1 Im/W 0.33/0.62 445 h 6 HIM-1 ETM-2 2.6 V 4.6 V 21.3 cd/A 14.5 Im/W 0.33/0.62 440 h 7 HIM-2 ETM-1 2.8 V 5.1 V 18.2 cd/A 11.2 Im/W 0.34/0.62 390 h 8 HIM-2 ETM-2 2.7 V 4.8 V 20.2 cd/A 13.2 Im/W 0.34/0.63 375 h The electron transport material used in the electron transport layer (ETL) is either AlQ ₃ according to the prior art or, according to the invention, triphenylheptaazaphenalene (ETM-1) or trimesitylheptaazaphenalene (ETM-2). Table 1

HTM-1 NPB

HIM-1 HIM-2 (state of the art)

H1 D1

ETM-1 ETM-2

AlQ ₃ (state of the art) Table 2 E.g. HIL ETL Operating voltage Voltage for 1000 cd/m ² Efficiency at 1000 cd/m ² Power efficiency at 1000 cd/m ² CIE x/y at 1000 cd/m ² Lifespan for 25000 cd/ ^m2 3 HIM-1 _AlQ3 2.7V 4.8V 18.9 cd/A 12.4 In/W 0.34/0.63 410 h 4 (compare) HIM-2 _AlQ3 2.8V 5.0V 17.1 cd/A 10.7 In/W 0.34/0.62 355 hours 5 HIM-1 ETM-1 2.8V 5.0V 19.2 cd/A 12.1 In/W 0.33/0.62 445 hours 6 HIM-1 ETM-2 2.6V 4.6V 21.3 cd/A 14.5 In/W 0.33/0.62 440 hours 7 HIM-2 ETM-1 2.8V 5.1 V 18.2 cd/A 11.2 In/W 0.34/0.62 390 hours 8th HIM-2 ETM-2 2.7V 4.8V 20.2 cd/A 13.2 In/W 0.34/0.63 375 hours

Claims (15)

Organic electronic device containing cathode, anode and at least one organic layer which is arranged between cathode and anode and which contains at least one compound according to formula (3), formula (4), formula (5) or formula (6),

where the following applies to the symbols and indices used: Y is, on each occurrence, the same or different, a single bond or a divalent group, selected from the group consisting of B(R ¹ ), C(R ¹ ) ₂ , NR ¹ , O, S, C(=O), C(=C(R ¹ ) ₂ , S(=O), S(=O) ₂ , P(=O)(R ¹ ) ₂ , or a divalent aromatic or heteroaromatic ring system with 5 to 18 aromatic ring atoms, which can be substituted with one or more radicals R ¹ ; R is the same or different in each occurrence, D, F, Cl, Br, I, CHO, N(R ¹ ) ₂ , N(Ar) ₂ , C(=O)Ar, P(=O)(Ar) ₂ , S(=O)Ar, S(=O) ₂ Ar, CR ¹ =CR ¹ Ar, CN, NO ₂ , Si(R ¹ ) ₃ , B(OR ¹ ) ₂ , B(R ¹ ) ₂ , B(Ar) ₂ , B(N(R ¹ ) ₂ ) ₂ , OSO ₂ R ¹ , a straight-chain alkyl, alkoxy or thioalkoxy group with 1 to 40 C atoms or a straight-chain alkenyl or alkynyl group with 2 to 40 C atoms or a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy or thioalkoxy group with 3 to 40 C atoms, each with one or more radicals R ¹ can be substituted, with one or more non-adjacent CH ₂ groups being replaced by R ¹ C=CR ¹ , C=C, Si(R ¹ ) ₂ , Ge(R ¹ ) ₂ , Sn(R ¹ ) ₂ , C =O, C=S, C=Se, C=NR ¹ , P(=O)(R ¹ ), SO, SO ₂ , NR ¹ , O, S or CONR ¹ can be replaced and where one or more H- Atoms can be replaced by D, F, Cl, Br, I, CN or NO ₂ , or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, each of which can be substituted by one or more radicals R ¹ , or an aryloxy- or heteroaryloxy group with 5 to 60 aromatic ring atoms, each of which may be substituted by one or more radicals R ¹ , or a combination of these systems; R ¹ is the same or different in each occurrence as H, D, F, Cl, Br, I, CHO, N(R ² ) ₂ , N(Ar) ₂ , C(=O)Ar, P(=O)(Ar ) ₂ , S(=O)Ar, S(=O) ₂ Ar, CR ² =CR ² Ar, CN, NO ₂ , Si(R ² ) ₃ , B(OR ² ) ₂ , B(R ² ) ₂ , B(N(R ² ) ₂ ) ₂ , OSO ₂ R ² , a straight-chain alkyl, alkoxy or thioalkoxy group with 1 to 40 carbon atoms or a straight-chain alkenyl or alkynyl group with 2 to 40 carbon atoms or a branched one or cyclic alkyl, alkenyl, alkynyl, alkoxy or thioalkoxy group with 3 to 40 carbon atoms, which can each be substituted with one or more R ² radicals, where one or more non-adjacent CH ₂ groups are replaced by R ² C=CR ^2, C≡C, Si(R ² ) ₂ , Ge(R ² ) ₂ , Sn(R ² )2, C=O, C=S, C=Se, C=NR ² , P(=O)(R ² ), SO, SO ₂ , NR ² , O, S or CONR ² can be replaced and one or more H atoms can be replaced by D, F, Cl, Br, I, CN or NO ₂ , or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, each of which may be substituted by one or more R ² radicals, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more R ² radicals, or a combination of these systems; In each occurrence, Ar is, identically or differently, an aromatic or heteroaromatic ring system with 5 to 30 aromatic ring atoms, which may be substituted with one or more non-aromatic radicals R ¹ ; Two Ar residues, which bind to the same nitrogen or phosphorus atom, can also be formed through a single bond or a bridge, selected from B(R ² ), C(R ² ) ₂ , Si(R ² ) ₂ , C=O, C =NR ² , C=C(R ² ) ₂ , O, S, S=O, SO ₂ , N(R ² ), P(R ² ) and P(=O)R ² , be linked together; In each occurrence, R ² is identical or different H, D or an aliphatic, aromatic and/or heteroaromatic hydrocarbon radical with 1 to 20 carbon atoms, in which H atoms can also be replaced by F; n is 0, 1, 2, 3, 4, 5 or 6; m is 1, 2 or 3, and wherein the organic electronic device is an organic electroluminescence device (OLED) or a light-emitting electrochemical cell (LEC). Organic electronic device Claim 1 , characterized in that R ¹ in formula (4) and formula (6) represents hydrogen. Organic electronic device Claim 1 or 2 , characterized in that the index n in compounds of the formula (3) and (4) is 0, 1 or 2, particularly preferably 0 or 1, very particularly preferably 0 and that the index m in the compounds of the formula ( 5) and (6) represents 1 or 2, particularly preferably 1. Organic electronic device according to one or more of the Claims 1 until 3 , characterized in that R in the compounds of formulas (3) to (6) is the same or different in each occurrence for F, N(R ¹ ) ₂ , N(Ar) ₂ , C(=O)Ar, P(= O)(Ar) ₂ , CN, NO ₂ , a straight-chain alkyl group with 1 to 10 carbon atoms or a branched or cyclic alkyl group with 3 to 10 carbon atoms, which can each be substituted with one or more radicals R ¹ , where one or more H atoms can be replaced by F or CN, or an aromatic or heteroaromatic ring system with 5 to 40 aromatic ring atoms, which can each be substituted by one or more R ¹ radicals. Organic electronic device Claim 4 , characterized in that R in the compounds of the formulas (3) to (6) is the same or different in each occurrence for F, CN, CF ₃ or an aromatic or heteroaromatic ring system with 5 to 30 aromatic ring atoms, each represented by one or more R ¹ may be substituted, with preferred aromatic or heteroaromatic ring systems being selected from the group consisting of phenyl, 2-, 3- or 4-pyridyl, pyrazinyl, 2-, 4- or 5-pyrimidinyl, 3- or 4 -Pyridazinyl, ortho-, meta- or para-biphenyl, ortho-, meta- or para-terphenyl, 2-fluorenyl, 2-spirobifluorenyl, 1-naphthyl, 2-naphthyl, anthracenyl, phenylanthracenyl, 1- or 2-naphthylanthracenyl, Binaphthyl, pyrenyl, fluoranthenyl, 2-, 3-, 4-, 5-, 6- or 7-benzanthracenyl, N-imidazolyl, N-benzimidazolyl, phenyl-N-benzimidazolyl, N-phenylbenzimidazolyl, phenyl-N-phenylbenzimidazolyl or combinations of these groups, which can each be substituted by one or more radicals R ¹ . Organic electronic device according to one or more of the Claims 1 until 5 , characterized in that all R radicals are chosen equally. Organic electronic device according to one or more of the Claims 1 until 6 , characterized in that in compounds of the formulas (3) to (6) Y is the same or different in each occurrence for a single bond or a divalent group selected from the group consisting of C(R ¹ ) ₂ , NR ¹ and a divalent aryl - or heteroaryl group with 5 to 14 aromatic ring atoms, which can be substituted with one or more radicals R ¹ . Organic electronic device containing at least one oligomer, polymer or dendrimer which contains one or more compounds according to formula (3) to (6) according to one or more of claim che 1 until 7 contains, where one or more radicals R represent bonds of the compound according to formula (3) to (6) to the polymer, oligomer or dendrimer. Organic electroluminescent device according to one or more of the Claims 1 until 8th , containing anode, cathode and one or more emitting layers, wherein at least one organic layer, which can be the emitting layer or another layer, contains at least one compound according to formula (3) to (6) or a corresponding oligomer, polymer or dendrimer , and further optionally containing further layers, each selected from one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, electron blocking layers, exciton blocking layers, charge generation layers and / or organic or inorganic p / n junctions, whereby these layers can also be doped. Organic electroluminescent device according to Claim 9 , characterized in that the compounds according to formula (3) to (6) are used as hole injection or hole transport material, in particular when at least one substituent R, preferably at least two substituents R, particularly preferably all three substituents R represent an electron-poor group. Organic electroluminescent device according to Claim 10 , characterized in that the substituents R are selected from the group consisting of CN, F, NO ₂ , CF ₃ , and substituted or unsubstituted electron-poor heterocycles, the electron-poor heterocycles being in particular selected from the group consisting of pyridine, pyrazine, pyrimidine, Pyridazine, triazine, pyrrole, imidazole, triazole and benzimidazole. Organic electroluminescent device according to one or more of the Claims 9 until 11 , characterized in that the compounds according to formula (3) to (6) are used as electron transport material or as hole blocking material in an electron transport layer or a hole blocking layer, in particular if the substituents R, the same or different, stand for an aromatic or heteroaromatic ring system in each occurrence , whereby the electron transport layer or hole blocking layer can also be doped. Organic electroluminescent device according to one or more of the Claims 9 until 12 , characterized in that the compounds according to formula (3) to (6) are used as charge generation material in a charge generation layer. Use of compounds according to one of the formulas (3) to (6) according to one or more of Claims 1 until 8th in organic electronic devices, wherein the organic electronic device is an organic electroluminescence device (OLED) or a light-emitting electrochemical cell (LEC). Method for producing an organic electronic device according to one or more of Claims 1 until 13 , characterized in that one or more layers are coated using a sublimation process and/or that one or more layers are coated using the OVPD (Organic Vapor Phase Deposition) process or with the aid of carrier gas sublimation and/or that one or more layers are made of solution or can be produced using any printing process.